The present invention concerns a process for improving the pour point of feeds containing linear and/or slightly branched, long (more than 10 carbon atoms) paraffins, to provide good yields on converting feeds with high pour points to at least one cut with a low pour point and a high viscosity index for oil bases.
The present invention also concerns a EU-1 zeolite from which a portion of the elements Al, Fe, Ga or B has been removed, for example dealuminated, a catalyst containing that zeolite, its use in converting hydrocarbons, and a process for reducing the pour point using that catalyst.
High quality lubricants are fundamentally important for the proper operation of modern machines, automobiles and trucks. However, the quantity of paraffins originating directly from untreated crude oil with properties which are suitable for use in good lubricants is very low with respect to the increasing demand in this sector.
Heavy oil fractions containing large amounts of linear or slightly branched paraffins must be treated in order to obtain good quality oil bases in the best possible yields, using an operation which aims to eliminate the linear or slightly branched paraffins from feeds which are then used as base stock, or as kerosene or jet fuel.
High molecular weight paraffins which are linear or very slightly branched which are present in the oils or kerosene or jet fuel result in high pour points and thus in coagulation for low temperature applications. In order to reduce the pour points, such linear paraffins which are not or are only slightly branched must be completely or partially eliminated.
This operation can be carried out by extracting with solvents such as propane or methyl ethyl ketone, termed dewaxing, with propane or methyl ethyl ketone (MEK). However, such techniques are expensive, lengthy and not always easy to carry out.
A further technique is selective cracking of the longest linear paraffin chains to form compounds with a lower molecular weight, part of which can be eliminated by distillation.
Because of their form selectivity, zeolites are among the most widely used catalysts. The idea underlying their use is that zeolitic structures exist which have pore openings which allow long linear or very slightly branched paraffins to enter their micropores but which exclude branched paraffins, naphthenes and aromatic compounds. This phenomenon leads to selective cracking of linear or very slightly branched paraffins.
Zeolite based catalysts with intermediate pore sizes such as ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-38 have been described for their use in such processes.
Processes using such zeolites can produce oils by cracking feeds containing less than 50% by weight of linear or linear or very slightly branched paraffins. However, for feeds containing higher quantities of these compounds, it has become apparent that cracking them leads to the formation of large quantities of products with lower molecular weights such as butane, propane, ethane and methane, which considerably reduces the yield of desired products.
In order to overcome these disadvantages, we have concentrated our research on developing catalysts which also encourage isomerisation of such compounds.
The invention provides a process for improving the pour point of a paraffinic feed comprising paraffins containing more than 10 carbon atoms, in which process the feed to be treated is brought into contact with a catalyst based on EU-1 zeolite and at least one hydro-dehydrogenating element, at a temperature which is in the range 170xc2x0 C. to 500xc2x0 C., a pressure in the range 1 to 250 bar and an hourly space velocity in the range 0.05 to 100 hxe2x88x921, in the presence of hydrogen in a proportion of 50 to 2000 l/l of feed.
EU-1 zeolite in its hydrogen form, termed H-EU-1, obtained by calcining and/or ion exchanging as synthesized EU-1, used in the process of the invention, and its synthesis are described in European patent EP-B1 0 042 226. That zeolite has the following molar composition: 0.5 to 1.5 R2O: T2O3: at least 10 XO2: 0 to 100 H2O, where R is a monovalent cation or 1/n of a cation with valency n, X is silicon and/or germanium, T is Al, Fe, Ga or B and the water is water of hydration which adds to the initial water present when R is H. This EU-1 zeolite is characterized by the following X ray diffraction table:
X ray diffraction table for zeolite in the form Naxe2x80x94Hxe2x80x94EU-1, i.e., partially in its hydrogen form and containing sodium.
EU-1 zeolite with structure type EUO, used in the present invention has a one-dimensional microporous network with pore openings delimited by 10 T atoms (tetrahedral atoms: Si, Al, Ga, Fe . . . ), with a pore diameter of 4.1xc3x975.7 xc3x85. This structure is described in xe2x80x9cThe Atlas of Zeolite Structure Typesxe2x80x9d, by W. M. Meier, D. H. Olson and Ch. Baerlocher, Fourth Edition, 1996. This zeolite also has wide lateral pockets along its principal channels with pore openings delimited by 10 T atoms (tetrahedral atoms: Si, Al, Oa, Fe . . . ) with dimensions of about 6.8xc3x975.8 xc3x85.
The term xe2x80x9cpore opening of 10 or 12 tetrahedral atoms (T)xe2x80x9d means pores constituted by 10 or 12 sides.
The process can advantageously convert a feed with a high pour point to a mixture (for example oil) with a lower pour point and, in the case of oil, a high viscosity index. It can also be applied to reducing the pour point of gas oils, for example.
Among others, the feed is composed of linear and/or slightly branched paraffins containing at least 10 carbon atoms, preferably 15 to 50 carbon atoms, and advantageously 15 to 40 carbon atoms. Heavy feeds contain paraffins essentially containing more than 30 carbon atoms and produce base stock; gas oils are lighter and contain paraffins containing 10-30 carbon atoms.
The isomerised products may contain about 65% to 80% of single-branched products and about 20% to 35% of multi-branched products. The term xe2x80x9csingle-branched productsxe2x80x9d means linear paraffins comprising a single methyl group, and the term xe2x80x9ctwo-branched productsxe2x80x9d means linear paraffins containing 2 methyl groups which are not carried by the same carbon atom. Thus xe2x80x9cmulti-branchedxe2x80x9d paraffins can be defined by extension.
Further, the catalyst comprises at least one hydro-dehydrogenating function, for example a group VIII metal (noble or non-noble) or a combination of at least one group VIII (non noble) metal or compound and at least one group VI metal or compound, and the reaction is carried out under conditions which will be described below.
Using the EU-1 zeolite of the invention under the conditions described above can produce products with a low pour point and oils with a high viscosity index, in good yields.
EU-1 zeolite has an Si/T atomic ratio in the range 5 to 600 and in particular in the range 10 to 300.
The global Si/T ratio of the zeolite and the chemical composition of the samples are determined by X ray fluorescence and atomic absorption.
The EU-1 zeolite used in the process of the invention can be obtained with the desired Si/T ratio for the catalytic application of the invention directly by synthesis by adjusting the operating conditions for synthesis. Then the zeolite is calcined and exchanged by at least one treatment using a solution of at least one ammonium salt to obtain the ammonium form of the zeolite which, once calcined, leads to the hydrogen form of the zeolite.
Advantageously, in other cases the EU-1 zeolite has undergone a treatment aimed at eliminating (removing) a portion of elements T, for example aluminium (in which case it is dealumination) so as to increase the low Si/T ratio obtained on synthesis.
This zeolite is obtained from as synthesised zeolite and thus contains silicon and an element T selected from the group formed by Al, Fe, Ga and B. A portion of elements T have been removed from the zeolite framework and advantageously they are extracted from the sample (they then pass into solution in the case of acid attack).
Thus the global Si/T atomic ratio of the zeolite is greater than that of the starting zeolite, the difference (increase) is at least equal to 10% of the Si/T ratio of the starting zeolite.
The surface Si/T atomic ratio (obtained by XPS) does not diminish, and generally it increases by a substantial amount.
The global Si/T atomic ratio is at least 10, preferably at least 20, or more preferably over 60, and generally EU-1 zeolites are used with Si/Al ratios of at most 600, preferably at most 300. Si/T ratios of 20 to 200 or even 20 to 100 are particularly advantageous.
The zeolite constitutes a further aspect of the invention.
The dealuminated EU-1 zeolite of the invention, in the preferred case where T is Al, can be prepared using two dealumination methods from as synthesised EU-1 zeolite containing an organic structuring agent. These methods are described below. However, any other method which is known to the skilled person can also be used. These methods described for aluminium (Al) can also be used for other elements T.
The first (preferred) method, direct acid attack, comprises a first calcining step carried out in dry air, at a temperature which is generally in the range 450xc2x0 C. to 550xc2x0 C., which eliminates the organic structuring agent present in the micropores of the zeolite, followed by a step in which the zeolite is treated with an aqueous solution of a mineral acid such as HNO3 or HCl or an organic acid such as CH3CO2H. This latter step can be repeated as many times as is necessary to obtain the desired degree of dealumination. Between these two steps, one or more ion exchange steps can be carried out using at least one NH4NO3 solution, to at least partially and preferably almost completely eliminate the alkaline cation, in particular sodium. Similarly, at the end of the direct acid attack dealumination step, one or more ion exchange steps may be carried out using at least one NH4NO3 solution to eliminate residual alkaline cations, in particular sodium.
In order to obtain the desired Si/Al ratio, the operating conditions must be correctly selected; the most critical parameters in this respect are the temperature of the treatment with the aqueous acid solution, the concentration of the latter, its nature, the ratio between the quantity of acid solution and the mass of the treated zeolite, the treatment period and the number of treatments carried out.
Dealumination can also be achieved using chemical dealuminating agents such as (by way of non exhausting examples) silicon tetrachloride (SiCl4), ammonium hexafluorosilicate [(NH4)2SiF6], and ethylenediaminetetra-acetic acid (EDTA), including its mono and disodium forms. These reactants can be used in solution or in the gaseous phase, for example in the case of SiCl4.
The second method, heat treatment (in particular using steam, by steaming)+acid attack, comprises firstly calcining in dry air at a temperature which is generally in the range 450xc2x0 C. to 550xc2x0 C., to eliminate the organic structuring agent occluded in the micropores of the zeolite. The solid obtained then undergoes one or more ion exchanges using at least one NH4NO3 solution, to eliminate at least a portion, preferably practically all, of the alkaline cation, in particular sodium, present in the cationic position of the zeolite. The zeolite obtained then undergoes at least one framework dealumination cycle comprising at least one heat treatment which is optionally and preferably carried out in the presence of steam, at a temperature which is generally in the range 500xc2x0 C. to 900xc2x0 C., and followed by at least one acid attack using an aqueous solution of a mineral or organic acid as defined above. The conditions for calcining in the presence of steam (temperature, steam pressure and treatment period), also the post-calcining acid attack conditions (attack period, concentration of acid, nature of acid used and the ratio between the volume of the acid and the mass of zeolite) are adapted so as to obtain the desired level of dealumination. For the same reason, the number of heat treatment-acid attack cycles can be varied.
In a variation of this second method, the acid attack step, i.e., treatment using a solution of an acid, can be replaced by treatment with a solution of a chemical dealuminating compound such as those cited above, for example, namely silicon tetrachloride (SiCl4), ammonium hexafluorosilicate [(NH)2SiF6], ethylenediaminetetra-acetic acid (EDTA), including its mono and disodium forms.
In the preferred case when T is Al, the framework dealumination cycle, comprising at least one heat treatment step, optionally and preferably carried out in the presence of steam, and at least one attack step carried out in an acid medium on the EU-1 zeolite, can be repeated as often as is necessary to obtain the dealuminated EU-1 zeolite having the desired characteristics. Similarly, following the heat treatment, optionally and preferably carried out in the presence of steam, a number of successive acid attacks can be carried out using different acid concentrations.
In a variation of this second calcining method, heat treatment of the EU-1 zeolite containing the organic structuring agent can be carried out at a temperature which is generally in the range 500xc2x0 C. to 850xc2x0 C., optionally and preferably in the presence of steam. In this case, the steps of calcining the organic structuring agent and dealuminating the framework are carried out simultaneously. The zeolite is then optionally treated with at least one aqueous solution of a mineral acid (for example HNO3 or HCl) or an organic acid (for example CH3CO2H). Finally, the solid obtained can optionally undergo at least one ion exchange step using at least one NH4NO3 solution, to eliminate practically all of the alkaline cations, in particular sodium, present in the cationic position in the zeolite.
The modified EU-1 zeolite (and advantageously that in which the global to Si/T ratio is at least 20 or over 20) of the invention is at least partially, preferably practically completely, in its acid form, i.e., in its hydrogen (H+) form. The Na/T atomic ratio is generally less than 10%, preferably less than 5%, and more preferably less than 1%. Preferably, the modified EU-1 has a global Si/T ratio of 20 to 200, preferably 20 to 100.
The catalyst of the invention contains EU-1 zeolite with an Si/T ratio of at least 10, which may or may not be mixed with a matrix, and optionally at least one hydro-dehydrogenating element, which is a noble metal or a combination of at least one group VI metal or compound and at least one group VIII metal or compound.
The catalyst used in the process of the invention contains at least one hydro-dehydrogenating element, for example at least one group VIII metal. It may be a noble metal, advantageously selected from the group formed by Pt or Pd, which is introduced into the molecular sieve by dry impregnation or ion exchange, for example, or by any other method which is known to the skilled person, or it is introduced into the matrix.
The amount of metal thus introduced, expressed as the weight % with respect to the mass of molecular sieve engaged, is generally less than 5%, preferably less than 3%, and the amount of noble metal in the catalyst is generally less than 2% by weight.
The hydro-dehydrogenating element can also be a combination of at least one group VI metal or compound (for example molybdenum or tungsten) and at least one group VIII metal or compound (for example nickel or cobalt). The total concentration of group VI and group VIII metals, expressed as the metal oxides with respect to the support, is generally in the range 5% to 40% by weight, preferably in the range 7% to 30% by weight. The weight ratio (expressed as the metallic oxides) of group VIII metals to group VI metals is preferably in the range 0.05 to 0.8: more preferably in the range 0.13 to 0.5.
The element can also be rhenium and/or niobium, used alone or in combination with the group VIII and/or VI elements.
This type of catalyst can advantageously contain phosphorous, the content of which is generally less than 15% by weight, preferably less than 10% by weight, expressed as phosphorous oxide P2O5 with respect to the support.
When treating a real feed, the molecular sieve of the invention is first formed. In a first variation, the molecular sieve can have at least one group VIII metal, radical selected from the group formed by platinum and palladium, deposited on it, and it can be formed by any technique which is known to the skilled person. In particular, it can be mixed with a matrix, which is generally amorphous, for example a moist alumina gel powder. The mixture is then formed, for example by extrusion through a die. The amount of molecular sieve in the mixture obtained is generally in the range 0.5% to 99.9%, advantageously in the range 5% to 90% by weight, with respect to the mixture (molecular sieve+matrix) and preferably in the range 10% to 90%, more preferably in the range 20% to 70%.
In the remaining text, the term xe2x80x9csupportxe2x80x9d is used to describe the molecular sieve+matrix mixture.
Forming can be carried out with matrices other than alumina, such as magnesia, amorphous silica-aluminas, natural clays (kaolin, bentonite, sepiolite, attapulgite), silica, titanium oxide, boron oxide, zirconia, aluminium phosphates, titanium phosphates, zirconium phosphates, and mixtures thereof. Techniques other than extrusion, such as pelletization or bowl granulation, can be used.
The group VIII hydrogenating metal, preferably Pt and/or Pd, can also very advantageously be deposited on the support using any process which is known to the skilled person which can deposit metal on the molecular sieve. Competitive cation exchange can be used, with ammonium nitrate as the preferred competing agent, the competition ratio being at least about 20 and advantageously about 30 to 200. When platinum or palladium is used, a platinum tetramine complex or a palladium tetramine complex is normally used: these latter are almost completely deposited on the molecular sieve. This cation exchange technique can also be used to deposit the metal directly on powdered molecular sieve before mixing it with any matrix.
Deposition of the group VIII metal(s) is generally followed by calcining in air or oxygen, usually between 300xc2x0 C. and 600xc2x0 C. for 0.5 to 10 hours, preferably between 350xc2x0 C. and 550xc2x0 C. for 1 to 4 hours. Reduction in hydrogen can then follow, generally at a temperature which is in the range 300xc2x0 C. to 600xc2x0 C. for 1 to 10 hours, preferably in the range 350xc2x0 C. to 550xc2x0 C. for 2 to 5 hours.
The platinum and/or palladium can also be deposited not directly on the molecular sieve, but on the matrix (alumina binder) before or after forming, by anion exchange with hexachloroplatinic acid, hexachloropalladic acid and/or palladium chloride in the presence of a competing agent, for example hydrochloric acid. As before, after depositing the platinum and/or palladium, the catalyst is generally calcined then reduced in hydrogen as indicated above.
The non noble group VIII metals or an association of oxides of non noble group VI and VIII metals, comprising the hydro-dehydrogenating function, can be introduced into the catalyst at various stages of the preparation and in various fashions.
It can be introduced only in part (for associations of group VI and VIII metal oxides) or completely on mixing the molecular sieve of the invention with the gel of the oxide selected as the matrix. It can be introduced using one or more ion exchange operations on the calcined support constituted by the molecular sieve of the invention dispersed in the selected matrix, using solutions containing precursor salts of the selected metals when these belong to group VIII. They may be introduced by one or more impregnation operations carried out on the formed and calcined support, using a solution of precursors of oxides of metals from group VIII (in particular cobalt or nickel) when the precursors of oxides of metals from group VI (in particular molybdenum or tungsten) have been introduced first on mixing the support. Finally, it can be introduced by one or more impregnation operations carried out on the calcined support constituted by a molecular sieve of the invention and the matrix, using solutions containing the precursor of the oxides of metals from groups VI and/or VIII, the precursors of oxides from group VIII metals preferably being introduced after those of group VI or at the same time as the latter. Impregnation methods lead to a deposit of group VIII metal essentially on the binder.
When the metal oxides are introduced in a plurality of impregnation steps using the corresponding precursor salts, an intermediate calcining step must be carried out at a temperature in the range 250xc2x0 C. to 600xc2x0 C.
Molybdenum impregnation can be facilitated by adding phosphoric acid to the ammonium paramolybdate solutions.
The mixture is then formed, for example by extrusion through a die. The amount of molecular sieve in the mixture obtained is generally in the range 0.5% to 99.9%, advantageously in the range 10% to 90% by weight with respect to the mixture (molecular sieve+matrix), preferably in the range 20% to 70%.
Deposit of the final metal is generally followed by calcining in air or in oxygen, usually between 300xc2x0 C. and 600xc2x0 C. for 0.5 to 10 hours, preferably between 350xc2x0 C. and 550xc2x0 C. for 1 to 4 hours.
It is then generally followed by sulphuration of the catalyst before bringing it into contact with the feed, using any method known to the skilled person. Thus in this case the catalyst advantageously contains sulphur.
The catalyst of the invention is used to convert hydrocarbons, in particular to reduce the pour point as will be defined below.
The process for reducing the pour point as defined below can also be carried out using a catalyst containing a EU-1 zeolite, obtained by synthesis, with the formula described above, in particular with a Si/T ratio of 5 to 600, advantageously 10 to 300. Zeolites with Si/T ratios of less than 10 are thus included.
Feeds which can be treated using the process of the invention are advantageously fractions with relatively high pour points the values of which are to be reduced.